Continuous Saponification and Neutralization Systems

Timothy Kelly
WF North America, Kansas Cify, Kansas, USA

The objective of this chapter is to provide an updated overview of continuous saponification and neutralization systems. Included are hndamental principles of operation, an overview of equipment and systems technology, and a review of commercially available systems.

Introduction
The commercial soap making systems available today are the result of a long evolution of technology advances. According to ancient Roman legend, soap got its name from Mount Sapo, where it was first made by accident as the result of the tallow from animal sacrifices reacting with the ashes from the burned wood to produce a mixture capable of cleaning clothes better. As the centuries progressed, soap making evolved into a batch process where animal fats and vegetable oils were boiled with ashes, soda ash, or caustic soda in small kettles to produce crude soap. T satisfy increasing demand, larger batches o were produced by what today is commonly called the kettle soap making process. Continuous soap making began in the mid-1940s with the development of processes for converting fats and oils into fatty acids via a hydrolysis reaction carried out under high pressure and temperature. The fatty acids, with the glycerine from the hydrolysis reaction removed, were reacted with a caustic soda, water, and salt blend to produce soap in a continuous fashion. This method of manufacture is referred to as continuous neutralization. To save energy and to improve yields, technology hrther advanced with the development of continuous processes for reacting neutral fats and oils directly with caustic soda to produce soap and glycerine. An important part of these processes was the technology employed to remove the glycerine from the soap. This method of manufacture is referred to as continuous saponification. Whether soap is produced via fatty acid neutralization systems or continuous saponification systems, the major soap making equipment manuhcturers have continued to improve these technologies. In recent years, commercially available systems were modified to reduce energy consumption, to reduce changeover time and losses, to reduce plant maintenance, to increase flexibility, and to improve plant layouts. The information that follows provides an overview of the principles behind these technologies and the manufacturing systems available in the market today.

Continuous Saponification
Overview
The continuous saponification method for making soap is also called neutral fadoil saponification or h l l boiled saponification. This is globally the most widely used process for soap making. In this process, a blend of fat and oil is reacted with caustic soda (NaOH) to produce soap and glycerine. The glycerine and other water soluble impurities are removed from the soap. Once the soap is adjusted for final alkalinity, it is sent to storage to await hrther processing. A simplified block diagram of the process 223

224 0 T. Kelly
is shown in Fig. 8.1. The reader is referred to the Appendix for a summary of the definitions and terminology used in this diagram and throughout the remainder of this chapter. The simplified block diagram shows the major unit operations required in the continuous saponification process. These operations and their purposes are: MeteringlDosing-This system. operation provides for an accurate addition of all raw materials into the

Saponification-This operation provides for a complete reaction of the fats/oils with caustic to produce soap and glycerine. Cooling and Spent Lye Separation, Washing and Half Spent Lye Separation, and Lye and Neat Soap Separation-These three operations combine to remove glycerine and other water soluble impurities from the soap and to establish the NaCl and N a O H content in the soap to neutralization. Neutralization-This system reduces excess N a O H in the finished soap, and also provides for the addition of minor ingredients such as antioxidants into the soap prior to storage. A simplified flowsheet for a typical plant is shown in Fig. 8.2. In this process, raw materials are metered into the reactor, the washing column, and the neutralizer. The reacted soap leaving the reactor is cooled with recycled spent lye from the static separator. Upon entering the static separator, soap and spent lye separate, with the soap exiting the top of the static separator and the spent lye exiting the bottom. The soap exiting the static separator has the glycerine removed by using wash lye in a countercurrent extraction column. Due to density differences, wash lye leaves the bottom of the wash column as half spent lye, and is recycled to the reactor. Soap exits the top of the wash column, and is then centrifuged to remove entrained wash lye. The centrihge lye is recycled back to the wash column. The centrifuged soap flows into a neutralizer where the alkalinity is adjusted by using a neutralizing agent, and any required minor ingredients such as an antioxidant are added.

Metering/Dosing
The accurate addition of raw materials into the saponification system is critical to soap composition control and problem free system operation. The purpose of the metering system is to continuously dose the proper amount of each raw material into the saponification, washing, and neutralization systems.

Raw Materials
Fats-The most common fat used globally is tallow. This tallow is typically either edible tallow or bleached and filtered lower grade tallow. Other suitable fats include palm oil or a combination of palm oil and palm oil stearin. The fat produces a longer chain length (1 6 to 18 carbons) soap used to provide good soap structure and slow but stable lather. Oils-Globally, coconut oil and palm kernel oil are the most commonly used oils. To assure good soap quality, these oils are most often of a refined, bleached, and deodorized grade. The oil produces shorter chain length (12 to 14 carbons) soap used to provide a fast, creamy lather. Caustic Soda-A caustic soda solution with a strength of 50% o f N a O H is utilized. Most commonly the caustic is a low salt (cl%),low iron version. Lower iron content helps to protect the color stability of the finished soap. The caustic soda provides the N a O H required to saponiFy the fadoils into soap and glycerine. The N a O H , along with the NaCl from the brine, provides the electrolyte required to achieve the neat soap/lye two phase separation critical to glycerine removal in the washing system. Soap with a slight excess of caustic improves the stability of the soap in storage tanks.

METERING

54%
TFM SOAP COOLING& SPENTLYE SEPARATION COOLING MIXER FLASH COOLER

SAPONIFICATION __c

54% TFM CRUDE

54%

62-63'10 LYE & NEAT SOAP SEPARATION

TFM NEUTRALIZATION

WASHING& HALF SPENT LYE SEPARATION WASHING COLUMN

DOSING SYSTEMS

REACTOR

CENTRIFUGES

CRUTCHER l l TURBODISPERSER

Fig. 8.1. Continuous Saponification System Diagram.

N
\n

SPENT
WAS FROM

STEAM

CENTRIFUGE FEED TANK

'

RAW MATERIALS FROM DOSING SECTION

WASHING

TURBO

NEUTRALIZING AGENT FROM DOSING SECTION

d
~

Fig. 8.2. Typical Continuous Saponification Plant (Courtesy Binacchi & Co.).

t : 0
\3

c3

Continuous Saponification and Neutralization Systems 0 227

Water-Water is used, in combination with caustic soda and brine, to provide the washing lye necessary to achieve the neat soap/lye two phase separation critical to glycerine removal in the washing system. The water is usually softened to remove excess water hardness. Water hardness components can cause the scaling of heat exchanger surfaces in the wash lye pre-heater. Brine-Usually 20% of NaCl in a watedbrine solution is utilized. However, some operations utilize a saturated brine solution (approximately 26% of NaCI). With either brine solution, the softening of the water used to make the brine helps to prevent heat exchanger scaling due to water hardness. The NaCl in the brine provides the electrolyte required to achieve the neat soap/lye two phase separation critical to glycerine removal in the washing system. It also provides the finished neat soap with NaCl level important for optimal soap viscosity and flowability. Fatty Acid-Fatty acid can be utilized for neutralizing excess NaOH in the soap neutralization system. Many plants will react the excess NaOH with the same fat or oil used in the saponification system.

CriticalMetmd Smams The raw materials are combined to form several important flow streams into the operation.
Fadoil-The fat and oil are combined together into a single stream added into the saponification system. The ratio of fat to oil is important to producing the proper quality soap. Formulations of fadoil vary from 5050 to 85: 15 tdlow/coconut oil. Reaction Lye-Caustic soda, brine, and water are combined to produce the reaction lye utilized in the saponification system. In some systems, the half spent lye from the bottom of the washing column is also combined in this stream. Avoid mixing the brine directly with the caustic soda to prevent the precipitation of salt from the mixture. Washing Lye-Caustic soda, brine, and water are combined to produce the washing lye utilized in the washing column. Again, avoid mixing the brine directly with the caustic soda to prevent the precipitation of salt from the mixture.

MeteringQuipment Several types of equipment are available for metering systems. Many older system designs used a multiheaded piston style metering pump with a common motor and drive shaft. Raw materials were supplied to the pump heads from individual level tanks. The primary advantage of this system was the ability to change all flow rates with one pump speed change. Individual stream flows were adjusted by changing the stroke length of the piston. With improvements in flow measurement capability, commercial equipment vendors developed improved metering performance by utilizing flow meters and either centrihgal or positive displacement pumps:
Centrihgal Pump Metering System-Figure 8.3 shows a typical metering system utilizing a centrihgal pump. Raw materials enter the pump after being strained through duplex strainers. A mass flow meter and a pressure control valve are used to accurately control the flow from the pump. The primary advantage of this system is the ability to meter multiple streams with one centrifugal pump. This minimizes capital required for the plant. Positive Displacement Metering System-Figure 8.4 shows a typical metering system utilizing a positive displacement pump. Again, raw materials enter the pump after being strained through duplex strainers. A mass flow meter and a variable frequency drive are used to control the pump speed to accurately control flow from the pump. The primary advantage of this system is it will allow a larger minimum and maximum flow rate range than the centrifugal pump metering system. The disadvantage of this system is the higher capital cost and larger equipment layout required.

228 OT. Kelly

TRANSFER PUMP GROUP

Fig. 8.3. Mauoni LB'ISCNT"Continuous Saponification Centrifugal Pump Metering System.

STRAINERS

METERING PUMP LOOPS

Fig. 8.4. Binacchi CSWE-3 Continuous Saponification Positive Displacement Pump Metering System.

Saponification
Saponification is the reaction of fats and oils with caustic soda to produce soap and glycerine. Completely converting all of the fats and oils into soap and glycerine is critical to the subsequent steps in the washing process. An incomplete reaction will not allow the separation of soap and lye in the washing system.

Continuous Saponification and Neutralization Systems 0 229

Sapont5cdtion Reaction The saponification reaction is a chemical reaction between the fatsloils and the N a O H present in the caustic soda. The equation for the reaction is:
Fadoil+ 3 N a O H

-+

3 Soap + Glycerine

From the reaction equation 1 mole of fadoil reacts with 3 moles of N a O H to produce 3 moles of sodium soap and 1 mole of glycerine. While the reaction may seem simple, it is actually a step wise reaction with 1 mole of N a O H reacting with the fadoil triglyceride to form a diglyceride, liberating 1 mole of sodium soap. The diglyceride then reacts with another mole of N a O H to form the monoglyceride, releasing another mole of sodium soap. The final step is the monoglyceride reacting with the third mole of N a O H to form the glycerine and 1 final mole of sodium soap. The saponification reaction is exothermic, releasing 60 cal/mole of fadoil reacted. The heat liberated from this reaction is used in the process to maintain the temperature in the saponification reactor.

Rate of Reaction The saponification reaction is a heterogeneous reaction since the initial reactants are not soluble in each other. Due to this heterogeneous nature, the reaction proceeds in three stages: a slow initial stage, a fast autocatalytic stage, and a slow final stage. Figure 8.5 shows the degree of saponification as a function of time.
Initial Stage-During the initial stage, the N a O H containing water and oil is slowly forming an emulsion. As the emulsion forms, it promotes better contact between the oil and water phases, increasing the rate of reaction. The initial stage of the reaction is slow because the relatively high electrolyte content of the water portion of the reaction mixture forces the soap into an insoluble form which is not able to emulsify the oil. During this part of the reaction, the reaction rate is effectively limited by the agitation present in the reaction vessel.

TIME

Fig. 8.5. Rate of Saponification.

230 0 T. Kelly
Autocatalytic Stage-In this stage, rapid reaction is taking place because the soap concentration has reached the point where soap micelles are beginning to form. The micelles solubilize unsaponified fat, and thus promote contact between the unreacted fat and the NaOH. Final Stage-In this stage, the reaction slows down as the concentration of reactants decreases. During this part of the reaction, the reaction rate is effectively limited by the agitation present in the reaction vessel.

Criticul Reuction Factors

To achieve complete saponification, reaction system designs must take into account several critical factors.

Mixing/Shearing-Intimate contact between the fadoil and the NaOH containing water phase is
critical to forming a fine emulsion to minimize the slow initial stage of the reaction. In addition, good mixing also promotes reaction during the slow final stage. Temperature-As a rule of thumb, the reaction rate of saponification will double for every 10C increase in temperature. Most saponification systems operate at 120 to 140C to achieve the fastest react ion times. Composition-A slight excess of caustic is required to complete the reaction. In addition, the correct electrolyte concentration is needed to achieve the proper soap phase. Too high an electrolyte content will slow the reaction rate due to a hard soap grain. Residence Time-Sufficient residence time must be provided to complete the reaction. With all of the other factors, noted above, controlled properly, a residence time of 10 to 15 minutes is sufficient.

Suponajicution &uipmmt
Several different commercial equipment systems are available for the saponification process. Each of these systems attempts to utilize the factors critical to good saponification, to achieve complete saponification in the shortest period of time required. Two types of reaction systems are common. One design pre-shears reactants in a high shear device, followed by reaction completion in a subsequent vessel. The other design is based on a stirred tank reactor principle where reactants are introduced into a recycled saponified soap stream to pre-solubilize the fatdoil in the soap phase. The fadsoap blend returns to a vessel where a continual stream of reacted soap is removed. Figure 8.6 is a simplified flowsheet of a design where the fadoils and the reaction lye mixture are introduced together into a high shear mixer to promote the formation of a fine emulsion critical to minimizing the slow stage of the reaction. The high shear mixer is followed by an agitated reaction vessel where the saponification reaction is completed. Details of the internals of the reaction vessel are shown in Fig. 8.7. This reaction system is capable of producing fully saponified soap in a short period of time. Figure 8.8 is a simplified flowsheet of a design where the fats/oils and reaction lye are introduced into a recycled saponified soap stream. The blend then proceeds through a non-agitated tubular reaction vessel where saponified soap exits continuously. This vessel is operated at high temperature (1 30C)and 3 bar pressure to prevent soap flashing, until the reacted soap mass is flashed in the separate flash cooler.

Continuous Saponification and Neutralization Systems 0 23 1

AGITATED REACT10N VESSEL

RECIRCULATION PUMP

REACTED
SnAP

PkflF!
Fig. 8.6.Typical High Shear Reaction System.

HIGH SHEAR MIXER (TURBO DISPERSER)

Fig. 8.7. ReactionVessel Details (Courtesy Soaptec srl).

232 O T . Kelly
SPENT LYE TO STORAGE AND TREATMENT PLANT STATIC SEPARATOR

FROM FEEDING GROUP

7
TUBULAR REACTOR

TO CONSTANT LEVEL TANK

FLASH COOLER

FROM WASHING COLUMN TRANSFER PUMP RECYCLE PUMP

b
TRANSFER PUMP

Fig. 8.8. Mazzoni LB'ISCNT" Continuous Saponification Plant ReactionKooling System.

Soap Washing/Extrac tion

The removal of glycerine and water soluble impurities takes place in the soap washing/extraction system. In addition to the removal of glycerine, this system is also responsible for establishing the NaCl and N a O H content of the soap exiting to the neutralization system. As depicted in the simplified block diagram of the process shown in Fig. 8.1, the key unit operations in this system are cooling and spent lye separation, washing and half spent lye separation, and lye and neat soap separation. The washing system begins with the cooling of the reaction soap mixture by a cooling mixer, flash cooler, or spent lye recycle stream, followed by spent lye separation. The key part of the system is a rotating disc contactor (RDC) liquid/liquid extraction column, where wash lye is used to extract the glycerine from the liquid soap, The final step is the centrifuging of entrained wash lye carried over with the soap from the top of the wash column. Two key principles are critical to understanding the operation of the washing system. The first is the concept ofsoap phase chemistry. The second is Wiper's Model for the distribution of NaCl and N a O H between the soap and lye phases. Each of these is discussed briefly.

Continuous Saponification and Neutralization Systems 0 233

Soap Phase Chemistry

From a chemistry point of view, once the saponification of fats and oils is completed, the continuous saponification process is a five component system consisting ofsoap, NaCI, N a O H , water, and glycerine. A five component phase diagram is required to represent this system. However, this is a complicated system so it is simplified to a three-component system consisting of soap, electrolyte (NaCI and NaOH), and solvent (water and glycerine).

Soap Phase Diagram Figure 8.9 is a phase diagram for 7525 tallow/CNO soap. The phase diagram depicts phases present at specific system compositions. The vertical axis represents the percentage of soap composition in the mixture. The horizontal axis represents the percentage of electrolyte in the mixture. The electrolyte shown on the phase diagram is reported as the percentage of NaCI. Since electrolytes have different graining efficiencies, the equation for calculating electrolyte value for NaCl and N a O H is:
%electrolyte (as %NaCI) = %NaCI + (1.2)
x

(%NaOH)

?he third component is water. The bottom left-hand part of the phase diagram represents 100% water. Of particular interest for the continuous saponification process is the neat soap single phase area and the neat s o a p l y e two phase area. In the neat soap-lye two phase region, the majority of the continuous saponification process operates. The removal of glycerine from the reacted soap depends on the washing system composition being controlled in this two phase region. Once soap exiting the centrifuges has the final alkalinity adjusted in the neutralization system, the neat soap single phase is achieved. The approximate operating points of the continuous saponification system are shown on the phase diagram.

Limit Lye Concentration The left hand side of the neat soap-lye two phase region is known as the limit lye concentration. At the limit lye concentration, if electrolyte decreases, soap begins to dissolve in the lye, and the three phase neat soapnigre-lye region is present. Further electrolyte decreases will enter into the two phase neat-nigre region. The location of the limit lye concentration on a phase diagram is a function of the fadoil blend composition. Fats and oils have a unique graining index which determines the limit lye concentration. Table 8.1 shows the graining index for typical fits and oils and their blends. The limit lye concentration is also a function of the system temperature. As temperature is increased, the limit lye concentration increases, meaning an increase in the temperature of the system will result in a loss of neat s o a p l y e separation. Another way to think of this is that the neat soap is more soluble in the lye at higher temperatures. Soap Grain Within the neat soap-lye two phase region, the grain of the soap varies with electrolyte content. Figure 8.10 shows three types of soap grain. A normal grained soap would be found near the limit lye concentration line. At lower electrolyte levels, the grain softens until no separation, is apparent. This is shown in the soft grained photo. As electrolyte is increased to the right hand side of the neat soap-lye region, the soap grain becomes harder. The harder grain of soap has whiter peaks and is more bunched. This hard grain of soap entraps more lye in the soap grains. Glycerine removal efficiency is best when normal grained soap is present.

234 0 T. Kelly

80-

SOAP

- NaCl - WATER
SYSTEM

Fig. 8.9. Illustrative Soap Phase Diagram.

Table 8.1. Graining Index Material Tallow Palm Oil Palm Kernel Oil (PKO) Coconut Oil (CNO) Grainins Index (%NaCI)
~~~

5-7
5-7

13-17
20 25
10 (use weighted average of high end value DIUS 10% safety factor) a

80/20T/PKO

Continuous Saponification and Neutralization Systems 0 235

Hard
Fig. 8.1 0. Soap Grains.

Normal

Soft

Wiper3Model The distribution of NaCl and NaOH in soap separated from a lye phase is critical to the proper operation of the continuous saponification system. The composition of the wash lye determines the NaCl and NaOH content of the centrifuged soap. In 1940, J.H. Wigner proposed a model to describe the distribution of NaCI, NaOH, and glycerine between the separated soap and lye phases. An excellent discussion of Wigner's model was done by Villela and Suranyi (Spitz, 1996). A graphical representation of the model is shown in Fig. 8.1 1. The model states:
Soap curds consist of a soap hydrate containing 66% of total fatty matter (TFM) mixed with enmeshed lye. The 66% of TFM soap hydrate can never be separated as a discrete phase, and the soap curds will always contain some enmeshed lye. Electrolytes are present in the enmeshed lye and in the separated lye, but not in the hydration water of the soap hydrate. Both the electrolyte content of the enmeshed lye and the separated lye are identical. The sum of the hydration water plus enmeshed lye is the lye-in-soap. Glycerine is present in all of the aqueous phases at the same concentration, including the water of hydration.

To illustrate the power of this model, a simple calculation example is presented.

236 OT. Kelly

I
66% TFM Hydrate
~~ ~

Grained Soap Soap Curd

I
Separate

Anhydrous Soap

I
Example 7

Hydration Water 0% NaCl 0% NaOH Z% Glvcerine

Enmeshed Lye Le Y X% NaCl X% NaCl Y% NaOH Y% NaOH Z% Glvcerine Z% Glvcerine

Fig. 8.1 1. Graphical Representation of Wigners Model.

Assume 1000 kg of 62% o f T F M neat soap with 0.5% of NaCl was centrifuge separated from a lye solution. Calculate the NaCl content of the separated lye.

Solution
First the amount of 66% of hydrated soap must be calculated. This is done as follows: Hydrated soap
= (1 000 kg) x (0.62 TFM)I(0.66 TFM in hydrated soap) = 939.39 kg soap hydrate

If 939.39 kg of the neat soap is hydrated soap, the remainder is enmeshed lye. The amount of enmeshed lye is: Enmeshed lye
= 1000 kg-939.39 kg = 60.6 1 kg enmeshed lye

All of the NaCl in the neat soap is contained in the enmeshed lye. The concentration of the NaCl in the enmeshed lye is:
%NaC1 in enmeshed lye
= (1000 kg) x (0.5% NaCI)I(60.61 kg enmeshed lye) = 8.25% NaCl in the enmeshed lye

Since the composition of the enmeshed lye is the same as the separated lye, the NaCl content of this lye is 8.25%. The above example shows the detailed calculations for NaCI. Similar calculations can be made for NaOH. In general, divide the total amount of NaCl in the neat soap by 0.06 to obtain the maximum amount of NaCl in the washing lye. From a practical experience standpoint, the following values apply to the relationship of NaCl and NaOH in the soap and separated lye: For every 1% of NaCl in the washing lye, 0.066% of free NaCl exists in the neat soap. For every 1% of NaOH in the washing lye, 0.07% of free NaOH exists in the neat soap.

Continuous Saponification and Neutralization Systems 0 237

Glycerine Washing Equipment

The washing system begins with thecooling ofthe reaction soap mixture followed by spent lye separation. The key part of the washing system is an RDC liquid/liquid extraction column, where wash lye is used to extract the glycerine from the liquid soap. The final step in the system is the centrifuging ofentrained wash lye carried over with the soap from the top of the wash column. Each of these systems plays a critical role in removing the glycerine from the saponified soap.

Cooling and Spent Lye Removal

Since most saponification systems operate at temperatures between 120 and 140"C, reducing the saponified soap temperature is necessary to achieve the neat soap and lye separation required for the removal of glycerine. Traditionally, this temperature reduction was accomplished in a vessel called a cooling mixer. Saponified soap entering the cooling mixer is cooled by water flowing through tubes inside the agitated vessel. The 85C temperature of soap is controlled by regulating the flow of cooling water through the tubes. The cooled soap/lye stream then flows into a static separator where residence time is provided to allow the soap to separate from the spent lye. From the static separator, spent lye leaves the washing system for further glycerine recovery processing. The soap proceeds on to the washing column. While the cooling mixer system was a standard offering in the industry for many years, recent technology advances have replaced it. Two types of systems are currently produced by equipment manufacturers. Flash Cooler-Mazzoni LB offers a flash cooler system, shown previously in Fig. 8.8. This system uses the temperature available in the soap from the saponification system to flash cool the soap/lye mixture prior to the static separator. The water that flashes off as steam is available to preheat raw materials. The flashed soap is then pumped to a static separator for the removal of the spent lye. The advantages of this system over the cooling mixer are higher glycerine in the spent lye (40%), increased energy efficiency, and reduced mechanical reliability issues. Cooled Spent Lye Recycle-Binacchi and others offer a cooled spent lye recycle system, shown in Fig. 8.12. In this system, a recycled stream of spent lye from a static separator is pumped through a plate and frame heat exchanger where it is cooled. The cooled spent lye is injected into the saponified soap leaving the reactor. The spent lye and soap mixture is mixed in a static mixer, and then sent to the static separator for the removal of the spent lye. The advantages of this system over the cooling mixer are reduced mechanical reliability issues and reduced plant layout.

Washing and Half Spent Lye Removal The key part of the glycerine removal system is the wash column shown in Fig. 8.13. The wash column is an RDC countercurrent liquidlliquid extraction column. Unwashed soap and entrained lye from the static separator enter the bottom of the wash column. Wash lye enters near the top of the column. Since the soap is less dense than the wash lye, soap rises to the top of the column and overflows as washed soap to the centrifuges. Wash lye proceeds to the bottom of the column, where it exits as half spent lye. Lye from the centrifuges is recycled to the top portion of the column. Figure 8.14 shows the internal details of the top and bottom of the wash column. The column consists of a series of mixing and settling zones known as extraction stages. Each stage contains a stator ring of metal attached to the inside diameter of the vessel and a flat rotating disc attached to an agitator shah which runs most of the length of the column. Most wash column designs have 40 of these extraction stages. As unwashed soap moves up the column, it is subjected to sequential mixing and separating from the rotating discs and stator rings, respectively. This series of mixing and separating
stages provides for the removal of glycerine from the soap.

238 OT. Kelly

Fig. 8.1 2. Binacchi "CSWE-3"ContinuousSaponification Cooled Spent Lye Recycle System.

Fig. 8.1 3. RDC Column (Courtesy SOAPTEC srl).

Continuous Saponification and Neutralization Systems 0 239

Fig. 8.14. RDC Details (CourtesySOAPTEC srl).

Lye and Neat Soap Separation The soap exiting the top of the wash column entrains with it approximately 15-20% of wash lye. The final step in the soap washing system is centrifuging the entrained wash lye and recycling it back to the top of the wash column. The neat soap, with the lye removed, proceeds to the neutralization system. The centrifuge is specifically designed for soap and lye service. A typical centrifuge arrangement is shown in Fig. 8.15. The soap and entrained wash lye enter the centrifuge through a feed pipe which directs the flow to the bottom of the bowl. The bowl, spinning at approximately 5000 redminute, separates the soap and lye. Lye travels the outside part of the bowl to an impeller paring disc where it exits and returns to the top of the wash column. Neat soap travels to the center of the bowl and proceeds to another impeller paring disc where it exits to the neutralization system. Back pressure valves on the soap and lye outlets are used to maintain the proper separation of lye from the soap. Centrifuge designs were improved to increase mechanical reliability and to enable capacities of 8000 kg/hour of neat soap at 62% of TFM. Most continuous saponification systems are equipped with an extra centrifuge to allow for cleaning and repair.
GIycerinc WmbingEfiiency A properly controlled washing system will leave approximately 0.1-0.2% of glycerine in the neat soap.
Several key factors are critical to good glycerine removal:

The electrolyte in the washing lye should be close to the limit lye concentration. The electrolyte must be adjusted for the fadoil blend being utilized. With this normal grain soap (versus hard
grain), maximum glycerine removal is achieved. Increasing the number of extraction stages in the wash column increases glycerine removal. Most wash columns in systems today contain 40 stages of extraction.

The wash column agitator speed should be properly set via experimentation. Slow agitator speed
provides inadequate mixing. High agitator speed causes back mixing between stages and poor separation.

240 0 T. Kelly

Fig. 8.1 5. Soap/Lye Centrifuge Arrangement.

Incoming washing lye glycerine content must be below 0.3%. Salt is recovered in the glycerine recovery process and is recycled back to the continuous saponification system. O n e must control glycerine content in the salt to avoid excess glycerine in the wash lye. The washing ratio/bulk of lye can be varied to change glycerine removal. Both of these measures are indications of the amount ofwash lye used per unit of soap produced.

Neutralization
The final step in the continuous saponification process is the adjustment of the alkalinity of the neat soap leaving the centrifuges. Typically, the centrifuged neat soap has a caustic level of 0.2-0.3% of N a O H , with the exact amount being determined by the wash lye N a O H concentration. The N a O H is reduced to a final level set by the finished soap customer specifications, usually 0.01-0.08Yo.The reduction of the excess N a O H is accomplished by adding either a fatty acid or the same lauric oil used in the saponification process.

Neutralization Equipment The equipment systems used in the final neutralization step employ designs similar to the saponification systems. Figure 8.16 is a drawing of a typical neutralization system. Soap from the centrihges enters the neutralization vessel. A recycled soap stream from the neutralizer is pumped through a high shear mixing device known as a turbodisperser. Neutralizing agent is added into the high shear mixer. The purpose of the high shear mixer is to provide intimate mixing between the N a O H in the soap and the neutralizing agent. The intimate mixing speeds the reaction rate. Product leaving the high shear mixer is returned to the neutralizer vessel. A continuous stream of finished specification soap is removed from the soap neutralizer vessel. Control of the finished soap N a O H level is achieved by means of a

Continuous Saponification and Neutralization Systems 0 24 1

p H control system. The p H control system varies the amount of fatty acid metered into the system to maintain a constant N a O H level in the finished soap. Most p H probes are of a self-cleaning design with provisions to remove the probes for maintenance/calibration while the plant is still operating.

Fig. 8.1 6. Binacchi"CSWE-3" ContinuousSaponificationNeutralizationSystem.

CommerciallyAvailable Systems
Throughout the previous discussion concerning the hndamental principles ofoperation and the overview of equipment and systems technology employed in continuous saponification processes, many examples shared come from commercially available systems. Today's available equipment has incorporated design improvements aimed at increasing energy efficiency, improving flexibility by reducing changeover times and product holdup times, reducing plant maintenance by simplifying equipment designs, reducing plant layout area requirements, and providing flexibility to operate systems without glycerine removal to allow for operation as a semiboiled soap process. Commercially available systems today are described briefly below.

M u m n i LB S.p.A.-SCNT-N Plant This system, shown in Fig. 8.17, was introduced to the market in 2001. The key design features include centrihgal metering pumps with mass flow meters, a tubular reactor system capable of reducing saponification holding time to 8-10 minutes, a flash cooler system to allow up to 40% of glycerine in the spent lye and reduced energy consumption (100 kg of 3 bar steam per 1000 kg of neat soap), and a tubular neutralizer design which can be used as a stand alone fatty acid neutralization system. Plant capacities are available from 3 to 20 tons/hour.

x -

y"
t : 0
9
F i
rJ

Fig. 8.17. Manoni LB 'SCNT-N"Continuous Saponification Plant.

Continuous Saponification and Neutralization Systems 0 243

Binaccbi Q Co.-CSWE 3 Plant This plant was depicted previously in Fig. 8.2. The key design features include positive displacement metering pumps with mass flow meters for improved metering accuracy, reducing plant layout size by the utilization of a vertical reactor system, and the recycling of cooled spent lye to reduce the saponification mixture temperature, allowing for a reduced plant layout and a reduced product hold-up. Energy consumption is estimated at 120 kg of 3-bar steam per 1000 kg of neat soap. Plant capacities are available from 2 to 16 tons/hour.

Sekz GmbH-KVN Plant

Similar in design to Binacchis CSWE 3 system, plant capacities are available from 0.3 to 13 tons/ hour.

Continuous Fatty Acid Neut raIization

Overview
As was mentioned at the beginning of this chapter, continuous soap making processes began in the mid1940s with the development of processes for converting fats and oils into fatty acids. The fatty acids, with the glycerine from the hydrolysis reaction removed, are reacted with a caustic soda, water, and salt blend to produce soap in a continuous fashion. This method of manufacture is referred to as continuous fatty acid neutralization.

Neutralization Reaction
The neutralization reaction is a chemical reaction between the fatty acids and the NaOH present in the caustic soda. The equation for the reaction is: Fatty Acid + NaOH

+ Soap + Water

From the reaction equation 1 mole of fatty acid reacts with 1 mole of NaOH to produce 1 mole of sodium soap and 1 mole ofwater. This reaction proceeds at a very fast rate compared to the saponification reaction. The important Factors for a good neutralization reaction are accurate raw material metering, high shear mixing of htty acid and NaOH to promote good interfacial area, operation with a slight excess of NaOH, and good temperature control. The neutralization reaction is exothermic, releasing 14 cal/mole of reacted Fatty acid. The heat liberated from this reaction is used in the process to maintain the temperature in the neutralization reactor.

Neutralization Equipment
Compared to the continuous saponification method for making soap, this process is very simple because no glycerine removal equipment is necessary. As with continuous saponification technology, fatty acid neutralization technology has continued to evolve. Improvements in metering accuracy, reactor designs, and process controls have continued to reduce utility requirements, improve flexibility, reduce maintenance, and reduce plant layout space requirements.

M-ni

LB SCT-SSCThcess

Shown in Fig. 8.18 is the Mazzoni SCT-SSCT process for continuous soap making. When used as the SCT process, this system provides for fatty acid neutralization. When used as the SSCT process, this same system operates as a neutral oil saponification system without glycerine removal, commonly referred to as a semiboiled soap process. The semiboiled soap process is discussed in greater detail in a subsequent chapter.

244 0 T. Kelly
In a fatty acid neutralization process, raw materials are metered into the neutralization reaction loop by a series of centrifugal pumps. Raw materials enter the pump after being strained through duplex strainers. A mass flow meter and a pressure control valve are used to accurately control the flow from the pump. The proper amount of brine, water, caustic soda, and fatty acid blend are injected into a high shear mixer known as a turbodisperser. A recycled soap stream from the tubular reactor is also injected into the turbodisperser. Both the temperature of the caustic soda/water and of the fatty acid are controlled via plate and frame heat exchangers, with operating set points established to maintain the desired neutralizer temperature. The turbodisperser provides the intimate mixing of the reactants to facilitate a complete and uniform reaction. The soap leaving the turbodisperser flows into the tubular reactor where a continuous stream of soap exits. A p H meter is located in the recycled soap loop. This p H meter controls a trim pump which allows for fine p H adjustment of the finished soap by using fatty acid. The tubular reactor is designed to operate under high pressure and temperature. O n e advantage of this process is the ability to close-couple the S C T neutralizer system with a vacuum dryer known as the SCT-C system. This close-coupled process is discussed in greater detail in Chapter 9.
Other Commercial Systems Binacchi also offers fatty acid neutralization systems. The CSFA plant, shown in Fig. 8.19, is a fatty acid neutralization system with positive displacement metering pumps and a series of two agitated reaction vessels. The CHBS system, shown in Fig. 8.20, is a flexible dual reactor system capable of producing both fatty acid neutralized soap and semi-boiled soap.

Fig. 8.1 8. Mauoni "SCT" Continuous Fatty Acid Neutralization or "SSCT" Neutral Fats/Oils Saponification without Glycerin Extraction.

Continuous Saponification and Neutralization Systems 0 245

Fig. 8.1 9. Binacchi CSFAContinuousSaponification for Fatty Acids.

Fig. 8.20. Binacchi CHBYContinuous Saponification for Fatty Acids - Neutral Fats.

246 0 T. Kelly

Summary
Whether the choice of soap making system is a saponification process, fatty acid neutralization process, or a semi boiled process, continuous methods of production have proven advantages over older batch processes. Continuous systems improve yields, reduce energy consumption, require less in-process inventory, reduce production cycle times, improve finished product quality/consistency, increase flexibility, and require smaller plant layouts. Todays commercially available systems have continued to improve these advantages. A summary of recent advances includes: Improved metering system designs which use the latest flow measurement technologies to increase metering accuracy and to improve finished product quality. Improved reactor designs which enable complete reaction with shorter residence time. Reaction times in some systems were reduced to 8-10 minutes. ?he reduced hold up times allow for simpler changeovers with less rework material. Increased flexibility of system designs. Many systems are now designed to be capable of producing both fatty acid neutralization soap and neutral oil saponification soap on the same system. This is critical as both raw material and finished by-product glycerine prices continue to fluctuate. These systems can also be directly coupled to vacuum drying systems to provide hrther flexibility and energy savings. Increased energy efficiency through the use of flash coolers and heat interchanges of raw material and in-process streams. Steam consumption has improved from 150 to 100 kg per 1000 kg of neat soap produced on some system designs. The flash cooler system produces spent lye glycerine content up to 40%, reducing energy requirements in the glycerine recovery process. Reduced plant maintenance through cooling mixer elimination, use of standard centrihgal and positive displacement pumps, and improved centrihge mechanical designs.

As raw material and energy prices increase, the design of soap making systems will continue to improve to respond to changing market needs.

Acknowledgments
I wish to thank Luis Spitz for his help and support in the development of the material presented. In addition, I wish to thank each of the companies who supplied the information on their continuous soap making equipment. Their names are acknowledged in the illustrations they provided.

References
Spitz, L. (ed.) Soaps and Detergents: A %eontical and Practical Review; AOCS Press: Champaign, IL, 1996; pp. 141-147. Wigner, J.H. Soap manufacture, Be CberniculProcesses; Chemical Publishing Co.: New York, 1940.

Further Reading
Pdmquist, F.T.E.Soap Technology-Basic and Pbysical Chemistry, Zander & Ingerstrom AB: Stockholm, Sweden, 1983. Woollatt, E. %e Manufacture of Soaps, Other Detergents and Glycerine; Ellis Horwood Limited: London, England, 1985.

Continuous Saponificationand Neutralization Systems 247

Appendix
Definitions and Terminology
Saponification
Saponification is the chemical reaction of fits and oils with caustic soda and brine to form soap and glycerine.

Washing
Washing is the removal of glycerine from soap by extraction with a brine, caustic soda, and water mixture in an extraction or washing column. The brine, caustic soda, water mixture is typically referred to as a lye.

Neutralization
Neutralization is the addition of fatty acid or fats to neat soap to reduce alkalinity.

Total Fatty Acid (TFA)/Total Fatty Matter (TFM)

Total fatty acid (TFA) is a measure of the fitty acid content present in a soap mixture. TFA does not indicate that free fatty acid is present, but is the amount of fatty acid present as soap molecules. TFA is also called TFM. The relationship between soap content and TFM content is: %TFM = % of sodium soap x 0.93.

Grain
When a sufficient amount of electrolyte (caustic soda and salt) is added to a soap-and-water mixture, the soap is converted to an insoluble form. Soap in this form is referred to as grainy neat soap, and has a grainy, lumpy texture similar to oatmeal. Sometimes graining is referred to as salting-out or splittingout the soap. At high electrolyte content, soap is grained out from the lye with little soap dissolved in the lye. As electrolyte content decreases, the grain becomes softer and soap in the lye increases. At low electrolyte levels, no separation of soap from the lye occurs.

Electrolyte
Electrolyte is the term used to refer to solutions of NaCl and NaOH. In soap making, electrolyte is generally reported in terms of percentage of NaCI. Since different electrolytes affect soap graining differently, the following equation is used to relate them: Yoelectrolyte (as NaCI) = %NaC1 + 1.2 x %NaOH.

Limit Lye Concentration (LLC)

LLC is the total electrolyte concentration at which the grained out soap begins to dissolve in the lye.
It is also the minimal concentration of total electrolyte in which soap cannot dissolve any further in the lye. LLC is also called limit lye, limit lye solubility, and is most commonly referred to as-graining index

(GI).
Washing Lye
Washing lye is a mixture of water, 50% of caustic soda, and 20% of brine which enters the top section of the countercurrent washing column.

248 0 T. Kelly

Half Spent Lye

Half spent lye is lye that leaves the bottom of the washing column and is recycled to the saponification reactor.

Spent Lye
Spent lye is glycerine enriched lye which leaves the system after the saponification reactor or washing system.

Centrifuged Lye
Centrifuged lye is lye separated by the centrifuge, and recycled back to the upper section of the washing column.

Crude Soap (Unwashed Soap)

Crude soap is the saponified soap mixture from the reactor entering the bottom of the washing column.

Curd Soap (Washed Soap)

Curd soap is the 52-54% of TFM soap leaving the top of the washing column and sent to the centrifuges.

Neat Soap
Neat soap is the 6 2 4 3 % ofTFM soap leaving the centrifuges.

Neutralized Neat Soap

Neutralized neat soap is neat soap neutralized with fatty acids or fats in the neutralizer to final N a O H content.

Washing Ratio
Washing ratio is the quantity of spent lye removed per quantity of neat soap produced.

Bulk of lye
Bulk of lye (BOL) is the quantity of spent lye removed per quantity of fats and oils saponified. BOL is roughly 1.5 times the washing ratio.